Wide range kinetic determination of peracid and/or peroxide concentrations

ABSTRACT

A use composition monitor determines the concentration of peracid and/or peroxide in a use composition using a kinetic assay procedure. A sample mixture containing a sample of the use composition, a diluent and at least one reagent is prepared and analyzed using, for example, an optical detector. Response data obtained by the detector is indicative of the optical absorbance of the sample mixture as a function of time. A processor analyzes the response data to determine a corresponding best fit linear relationship. Depending upon an expected concentration range, the initial absorbance and/or the slope of the best fit equation are used to calculate the concentrations of the peracid and peroxide in the use composition.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. patent applicationSer. No. 11/810,417, filed on Jun. 5, 2007 and titled “KINETICDETERMINATION OF PERACID AND/OR PEROXIDE CONCENTRATIONS.”

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is related to the following commonly assignedutility patent applications, all of which are filed concurrentlyherewith and all of which are hereby incorporated by reference in theirentireties: A) U.S. patent application titled “OPTICAL CELL” havingattorney docket number 29805.23.1, B) U.S. patent application titled“TEMPERATURE STABILIZED OPTICAL CELL” having attorney docket number29805.24.1, and C) U.S. patent application titled “METHOD OF CALIBRATIONFOR NONLINEAR OPTICAL SENSOR” having attorney docket number 29805.26.1.

FIELD OF THE INVENTION

The present invention relates to apparatus and methods for determiningthe concentrations of peracid and hydrogen peroxide in a usecomposition.

BACKGROUND

Antimicrobial compositions are used in a variety of automated processingand cleaning applications to reduce microbial or viral populations onhard or soft surfaces or in a body or stream of water. For example,antimicrobial compositions are used in various applications includingkitchens, bathrooms, factories, hospitals and dental offices.Antimicrobial compositions are also useful in the cleaning or sanitizingof containers, processing facilities or equipment in the food service orfood processing industries, such as cold or hot aseptic packaging.Antimicrobial compositions are also used in many other applicationsincluding but not limited to clean-in-place systems (CIP),clean-out-of-place systems (COP), washer-decontaminators, sterilizers,textile laundry machines, filtration systems, etc.

Whatever the application, an antimicrobial or “use” composition is acomposition containing a defined minimum concentration of one or moreactive components which exhibit desired antimicrobial properties. Onesuch category of active antimicrobial component are peracids, such asperoxycarboxylic acid (peracid), peroxyacid, peroxyacetic acid,peracetic acid, peroctanoic acid, peroxyoctanoic acid and others.

The concentration of active components in the use composition is chosento achieve the requisite level of antimicrobial activity. In usecompositions in which one or more peracids are the active component, andin the instance of a recirculating process, the concentration ofhydrogen peroxide tends to increase over time while the concentration ofperacid decreases. However, in order to maintain the requisite level ofantimicrobial activity, the amount of peracid in the use compositionmust be maintained at a defined minimum concentration. In addition, asthe amount of hydrogen peroxide in the use composition increases, theuse composition may exceed a defined maximum concentration of hydrogenperoxide in the solution. In some applications, for example bottlingline cleansing, the allowable amount of residual hydrogen peroxide issubject to government regulations. Once the hydrogen peroxideconcentration exceeds the maximum concentration, the spent usecomposition is discarded and a new use composition generated.

To ensure that the amount of peracid is maintained at or above someminimum concentration and to determine when the amount of hydrogenperoxide reaches or exceeds a maximum concentration, it is necessary todetermine the concentration of peracid(s) and hydrogen peroxide in theuse composition. In the past, to determine both the peracidconcentration and the hydrogen peroxide concentration in a usecomposition has required multiple time consuming manual titrations,several different reagents and relatively large volumes of usecomposition. Moreover, past devices and methods for determining bothperacid and hydrogen peroxide concentrations were effective over only anarrow range of concentrations.

SUMMARY

In general, the disclosure relates to apparatus and methods fordetermining the concentration of peracid and/or hydrogen peroxide in ause composition. The apparatus and/or methods measure the concentrationof peracid and/or the concentration of hydrogen peroxide in a sample ofthe use composition using a kinetic assay procedure.

In one aspect, the invention is directed to a method for determining aconcentration of peracid and/or peroxide within a use composition. Themethod includes selecting an expected concentration range within whichthe concentrations of the peracid and/or peroxide are expected to fall.In some embodiments, the expected range depends upon an applicationemploying the use composition. A sample which includes the usecomposition, a diluent, and one or more reagents is prepared within asample line. In some embodiments, the sample further includes an acid.In some embodiments, the step of preparing the sample can depend uponthe expected concentration range. The sample can be mixed within thesample line and delivered to an optical cell. An optical response of thesample mixture is measured to obtain response data indicative ofabsorbance of the sample as a function of time. The concentrations ofthe peracid and peroxide within the use composition are determined basedupon the response data. In some embodiments, the method used todetermine the concentrations of peracid and peroxide depends upon theexpected concentration value. Moreover, in some embodiments of themethod, a calibration step is included prior to execution of some or allof the steps. In addition, in some embodiments, the steps of mixing thesample, delivering the sample, and measuring the optical response can beperformed within a temperature-regulated local environment.

In another aspect a system for determining the concentrations of peracidand peroxide within a use composition over a wide concentration range isdisclosed. Such a system includes an optical detector for obtainingresponse data from a sample which comprises the use composition, adiluent, and at least one reagent. The response data is indicative ofthe concentrations of the peracid and peroxide within the usecomposition. A processor connected with the optical sensor is configuredto determine the concentration of the peracid and/or the peroxide basedupon the response data. An expected concentration range selected andstored within the processor determines which method the processor willuse to determine the concentrations of the peracid and/or peroxide. Insome embodiments, the optical detector can be a reduced-turbulencedetector. In addition, some embodiments include a laminar flow mixer formixing the sample prior to measurement by the optical detector.Moreover, in some embodiments, the optical detector and laminar flowmixer can be temperature regulated.

In some embodiments, methods and devices according to the inventionprovide for the determination of peracid and peroxide concentrationswithin a use composition. In particular, embodiments can provide suchdetermination across a wide range of concentrations. Thus, embodimentscan allow for the use of a single device or method in a variety ofapplications and locations. Moreover, some embodiments can be adaptedfor use under a wide range of operating conditions. In addition, someembodiments can provide improved precision within the expectedconcentration range.

The details of one or more embodiments of the invention are set forth inthe accompanying drawings and the description below. Other features ofthe invention will be apparent from the description and drawings, andfrom the claims.

BRIEF DESCRIPTION OF THE DRAWINGS

The following drawings are illustrative of particular embodiments of theinvention and therefore do not limit the scope of the invention. Thedrawings are not to scale (unless so stated) and are intended for use inconjunction with the explanations in the following detailed description.Embodiments of the invention will hereinafter be described inconjunction with the appended drawings, wherein like numerals denotelike elements.

FIG. 1 shows a schematic diagram illustrating an example embodiment ofuse composition monitor 200.

FIG. 2 is a flow chart illustrating a sequence (240) carried out by usecomposition monitor 200 to collect response data and determine theconcentration of peroxyacetic acid and/or hydrogen peroxide in a usecomposition.

FIGS. 3A-3C show plots of absorbance versus time, absorbance versusperoxide concentration, absorbance versus peracid concentration and rateof absorbance versus peroxide concentration, respectively, for a sampleiodide solution.

FIG. 4 is a flowchart illustrating a procedure by which a processordetermines the concentrations of peracid and hydrogen peroxide fromresponse data.

FIG. 5 is a flow chart illustrating a process by which a controllermonitors and/or controls the concentrations of peracid and/or ofhydrogen peroxide in the use composition.

FIG. 6 is a schematic diagram illustrating an exploded view of atemperature regulated flow optical sensor.

FIG. 7A illustrates a glass cell with an internal mixer, and FIG. 7B isa schematic diagram illustrating an exploded view of a temperatureregulated flow cell with two input ports and a glass cell having aninternal mixer.

FIG. 8 is a schematic illustrating a cross-sectional right side view ofan optical cell holder having a single input port.

FIG. 9 is a schematic illustrating a cross-sectional right side view ofan optical cell holder having two input ports.

FIG. 10 is a flow chart illustrating a procedure by which a processorcan determine the concentrations of peracid and hydrogen peroxide fromresponse data according to some embodiments.

FIG. 11 is a plot of optical density versus time for a plurality ofsamples prepared having different barrier volumes.

FIGS. 12A and 12B are plots of concentration versus time andconcentration ratio versus time, respectively, indicating the mixingprofile of a sample solution according to some embodiments.

FIG. 13 is a plot of optical density versus time of a plurality ofsamples pushed through the detector line.

FIG. 14 is a plot of the standard deviations of the recorded opticaldensities of the samples of FIG. 13.

FIG. 15 is a plot indicating the concentrations of peroxide and peracidof a set of calibration solutions according to some embodiments.

FIG. 16 is a collection of plots of optical density versus time for eachof the calibration solutions indicated in FIG. 15.

FIG. 17 is a contour plot representative of exemplary peracidconcentrations as a function of measured optical density and timederivative of optical density according to some embodiments.

FIG. 18 is a contour plot representative of exemplary peroxideconcentrations as a function of measured optical density and timederivative of optical density according to some embodiments.

FIG. 19 is a schematic of a reduced turbulence optical cell havingaccording to some embodiments.

FIG. 20 is a plot of optical density versus time for a plurality ofsample solutions illustrating response data subject to turbulence.

FIG. 21 is a plot of optical density versus time for a plurality ofsample solutions illustrating appropriate response data according tosome embodiments.

FIG. 22A is a perspective view of a cell body according to someembodiments.

FIG. 22B is a perspective view of a section of the cell body of FIG. 22Ataken along line B-B.

FIG. 23 is a front plan view of a temperature stabilized optical celland sample preparation area according to some embodiments.

FIG. 24 is a side plan view of the temperature stabilized optical celland sample preparation area of FIG. 23.

FIG. 25 is a perspective view of the temperature stabilized optical celland sample preparation area of FIG. 23.

DETAILED DESCRIPTION

The present invention relates to apparatus and/or methods fordetermining the concentrations of peracid and/or hydrogen peroxide in ause composition. The apparatus and/or methods measure the concentrationof peracid and/or the concentration of hydrogen peroxide (hereinafterreferred to simply as “peroxide” or H₂O₂) in a sample of the usecomposition using a kinetic assay procedure.

FIG. 1 shows a schematic diagram illustrating an example embodiment of ause composition monitor 200 and an optional controller 100. Usecomposition monitor 200 may monitor the use composition to determine thecontent of any selected analyte. As discussed herein, use compositionmonitor 200 determines the concentration of peracid and/or hydrogenperoxide in the use composition. For example, the use composition may bemonitored to ensure that the concentration of peracid satisfies at leasta minimum threshold concentration. The use composition may also bemonitored to determine when the concentration of hydrogen peroxideexceeds a maximum threshold concentration.

As used herein, the term “peracid” refers to any acid that in which thehydroxyl group (—OH) is replaced with the peroxy group (—OOH). Theperacid(s) may be C2-C18 peracid(s), such as C2 (peracetic) acid and C8(peroctanoic) acid. It shall be understood that the apparatus and/ormethods of the present invention may detect the combined presence of allperacids in a sample, whether the sample contains one or more than onedifferent peracids, and that the invention is not limited in thisrespect.

Peroxycarboxylic acids generally have the formula R(CO₃H)_(n). In someembodiments, the R may be an alkyl, arylalkyl, cycloalkyl, aromatic orheterocyclic group, and n may be one or two.

Peroxycarboxylic acids useful in this invention include peroxyformic,peroxyacetic, peroxypropionic, peroxybutanoic, peroxypentanoic,peroxyhexanoic, peroxyheptanoic, peroxyoctanoic, peroxynonanoic,peroxydecanoic, peroxylactic, peroxymaleic, peroxyascorbic,peroxyhydroxyacetic, peroxyoxalic, peroxymalonic, peroxysuccinic,peroxyglutaric, peroxyadipic, peroxypimelic and peroxysubric acid andmixtures thereof as well others known to those of skill in the art.

The concentrations of peracid and/or peroxide determined by usecomposition monitor 200 may be used, for example, as feedback tocontroller 100 to maintain the peracid concentration in the usecomposition within a predefined range and/or to cause the emptying ofthe use composition vessel and production of a new use composition whenthe hydrogen peroxide concentration exceeds the maximum peroxidethreshold concentration. If, for example, the concentration of peracidin the use composition decreases below a predetermined level, the usecomposition may be replenished by adding a concentrated peracidcomposition to the use composition. As another example, if theconcentration of peroxide in the use composition exceeds a predeterminedlevel, the use composition may be replenished by emptying the usecomposition vessel of the spent use composition and generating a new usecomposition.

In the embodiment shown in FIG. 1, use composition monitor 200 includesa sequential injection analysis (SIA) manifold under control of aprocessor 212. The SIA manifold includes a syringe pump 214, a holdingcoil 216, a multi-position (multi-port) valve 218, a static mixer 220and a detector 222. The SIA manifold is a device that enables automationof manual wet chemical analytical procedures. In other embodiments,other optical-based or electromechanical detectors could also be used,and the invention is not limited in this respect.

Multi-port valve 218 may be implemented using a computer controlledvalve that allows selection of one or more ports to intake (aspirate) orexpel (dispense) samples, reagents or carriers as necessary in aparticular application. Multi-port valve 218 is connected to receive asample of the use composition, at least one carrier and at least onereagent along lines 219A, 219B, 219C and 219D respectively. Multi-portvalve is also connected to a waste line 219E.

The resultant streams including the samples, reagents and carriers movethrough the system and into the detector 222 via appropriate tubing. Thetubing may be narrow bore tubing with, for example, an inside diameter(ID) of 0.5 mm to 2 mm. Suitable multi-port valves include Cheminertvalve Model C25-3184, C25-3186, C25-3188 or C25-3180 multi-port valveswith 4, 6, 8 and 10 positions, respectively, available from VICI ValcoInstruments Co. Inc., Houston, Tex. Another example of a suitable valveis the M-470 6-Way Medium Pressure Selection Valve available fromUpchurch Scientific, Oak Harbor, Wash.

In the embodiment shown in FIG. 1, software running on processor 212controls the system protocol resulting in aspiration of the sample,reagent(s) and carrier and their transport to detector 222 for analysis.Software running on processor 212 also analyzes response data receivedfrom detector 222 and determines the concentrations of peracid andperoxide in the use composition based on the response data.

Syringe pump 214 is preferably a computer controllable bi-directionalpump capable of measuring small volumes (as low as 5-10 μl, for example)with high precision. The syringe pump does not become contaminated asthe solutions are only drawn into holding coil 216 and not into thesyringe. An example suitable syringe pump is the MicroCSP-3000 availablefrom FIAlab Instruments, Bellevue, Wash. An example of other suitablepumps are the M6 or M50 syringe-free pumps available from VICI ValcoInstruments Co. Inc., Houston, Tex. However, it shall be understood thatany suitable pump may be used without departing from the scope of thepresent invention, and that the invention is not limited in thisrespect.

Holding coil 216 at various time throughout the measurement sequencetemporarily holds the sample, carrier and/or reagent(s) after they aredrawn in by syringe pump 214. A suitable holding coil may be cut from asuitable length of tubing; for example a 1 ml holding coil may be madeusing 220 cm of 0.030″ ID tubing. However, it shall be understood thatany suitable holding coil may be used without departing from the scopeof the present invention, and that the invention is not limited in thisrespect.

When syringe pump flow is reversed, the fluid volume temporarily storedin holding coil 216 flows from the holding coil 216 through themulti-port valve 218 and into the static mixer 220. Static mixerprovides thorough mixing of the sample, reagent and carrier to ensurethat the response data measured by the detector 222 leads to an accuratedetermination of the concentrations of peracid and peroxide in the usecomposition. The static mixer 220 may be implemented using anyconventional device designed to rapidly mix together two or more fluids.For example, static mixer 220 may be a piece of tubing with internalbaffles that cause flow reversal of the fluids to result in rapidmixing. Static mixer 220 may also be implemented using a knottedreactor, reaction coil, serpentine or other fluid mixing device known inthe art. An example baffle-type static mixer is the Series 120Individual Mixing Elements available from TAH Industries Inc,Robbinsville, N.J. However, it shall be understood that any suitablemixer may be used without departing from the scope of the presentinvention, and that the invention is not limited in this respect.

In some embodiments, the static mixer can be replaced with a laminarflow mixer. Laminar flow mixing is accomplished by allowing adjacentcomponents of the sample to bleed into one another as the sample isdriven through the sample line. Such a mixer can provide fornon-turbulent mixing of the sample. An appropriate laminar flow mixercan comprise a length of tubing. In some embodiments, the tubing iscoiled to preserve space and allow for stowing within the device. Insome embodiments, a laminar mixing coil comprising approximately 80inches of tubing is used to mix the sample within the sample line priorto reaching detector 222.

Detector 222 measures at least one characteristic of the sample mixtureindicative of the concentrations of peracid and/or hydrogen peroxide inthe use composition. The measurements obtained by detector 222 arereferred to herein as “response data.” Processor 212 determines theconcentration of peracid and/or peroxide in the use composition based onthe response data. In one embodiment, detector 222 is an opticaldetector that measures the transmittance and/or the absorbance of thesample. In that embodiment, the response data may be the opticaltransmittance data or optical absorbance data of the sample as afunction of time. In other embodiments, detector 222 may measure othercharacteristics indicative of the concentrations of peracid and/orperoxide in the sample, such as fluorescence, pH, oxidation-reductionpotential, conductivity, mass spectra and/or combinations thereof. Inthose embodiments, the response data would be the corresponding measuredcharacteristic at the appropriate points in time. Example detectors 222include photometric detectors operating in the visible, ultraviolet orinfrared wavelength range, although other luminescence detectiontechniques may also be used without departing from the scope of thepresent invention. One example of a suitable commercially availablephotometric detector can be assembled using a DH-2000 Deuterium TungstenHalogen Light Source, FIA-Z-SMA Flow Cell and USB4000 Miniature FiberOptic Spectrometer, all available from Ocean Optics Inc., Dunedin, Fla.Example embodiments of suitable optical detectors are also describedherein with respect to FIGS. 6-10. It shall be understood, however, thatany suitable optical detector may be used without departing from thescope of the present invention, and that the invention is not limited inthis respect.

In the case of an optical detector, the voltage response of the detectorcorresponds to the amount of the light transmitted through the samplemixture. Detector 222 thus essentially measures the change of the samplesolution optical properties within detector 222 as a function of time.The transmittance is the ratio of the intensity of light coming out ofthe sample (I) to intensity of light incident to the sample (I₀),T=I/I₀. Once the transmittance of the sample is measured, the absorbance(A) of the sample may be calculated. The absorbance or optical density(A) is a logarithmic function of the transmittance; A=−log₁₀ T=−log₁₀I/I₀=log₁₀ I₀/I. As is discussed in further detail below, the initialabsorbance of the sample (A₀) is indicative of the concentration ofperacid in the use composition and the sample absorbance variation overtime is indicative of the concentration of hydrogen peroxide in the usecomposition. However, as is further indicated, this relationship may nothold true across wide ranging use composition concentrations. Forexample, at higher concentrations, e.g. above 500 ppm peracid,concentration of peracid is a function of both initial absorbance and,to a lesser degree, absorbance over time. Accordingly, to provideinstruments capable of accommodating use with a wide concentrationrange, i.e. a range encompassing both concentration ranges describedabove, alternative methods must be utilized.

The reagent(s) and carriers may be selected to provide an analyticaltest that reproducibly generates accurate response data. In oneembodiment, the reagent may include a buffered iodide solution. In otherembodiments, such as a multiple reagent system, the reagents may includean iodide solution, such as potassium iodide, with the pH adjusted tothe alkaline range and a dilute acid such as acetic acid to adjust thepH of the reacting species to a pH less than approximately 6.5. Thecarrier may include water, deionized water or other appropriate carrier.However, it shall be understood that other suitable reagents andcarriers may also be used without departing from the scope of thepresent invention, and that the invention is not limited in thisrespect.

The molar concentration of the reagent(s) may depend upon the range ofexpected concentrations of peracid and peroxide in the use composition.For example, for a peracetic concentration in the use composition in therange of about 1500 to about 2000 ppm, the molar concentration of theperacid may be in the range of about 0.0197 to about 0.0263.

FIG. 2 is a flow chart illustrating a measurement sequence (240) carriedout by use composition monitor 200 to collect response data anddetermine the concentration of peroxyacetic acid and/or hydrogenperoxide in a use composition. In one embodiment, use compositionmonitor 200 may be programmed to determine the concentrations of peracidand hydrogen peroxide on a periodic basis. The frequency at whichmonitoring device 200 determines the concentration of peracid andhydrogen peroxide in the use composition is referred to herein as the“monitoring frequency.” For example, monitoring device 200 may beprogrammed to monitor the concentrations of peracid and hydrogenperoxide in the use composition every 15 minutes, every 30 minutes,every hour, every two hours, every day or other appropriate time. Themonitoring frequency/interval may vary depending on, among other things,the particular application to which the use composition is directed andthe corresponding threshold concentrations of peracid and hydrogenperoxide.

At the start (242) of each measurement sequence, processor 212 managespreparation of a reagent blank (244) and collects the voltage responseof the detector with the reagent blank (246). The reagent blank is avolume containing only the carrier and the reagent(s), i.e., the reagentblank does not include any use composition. The reagent blank allows thesystem to compensate for any variations in the reagent or the carrier,such as variations in color or other variations, which might affect thetransmittance of the sample mixture and thus the resulting voltageresponse of the detector. The voltage response of the detector measuredusing the reagent blank may then be used as a reference voltage duringcalculation of the absorbance of the sample mixture.

Processor 212 manages a sequence of drawing in of the carrier, reagent,dilute acid (if used), and use composition sample and dispensing themthrough the static mixer and into the detector to prepare the samplemixture (248). Once detector 222 receives the sample mixture, processor212 collects the response data from detector 222 (250). In the case ofan optical detector, the response data is the measured change in theoptical response of the detector over time. In one embodiment, detector222 measures response data by measuring the color change (e.g.,absorbance or transmittance) of the sample solution within detector 222as a function of time. In other words, the voltage response of detector222 as a function of time corresponds to the amount of light transmittedthrough the sample mixture and hence the color the of the sample mixtureas the chemical reaction progresses. The response data is indicative ofthe concentrations of peracid and hydrogen peroxide in the usecomposition.

The time frame during which processor 212 collects response data fromdetector 222 is referred to herein as the “measurement interval.” Thefrequency at which processor 212 collects the measurements of detector222 is referred to herein as the “measurement rate.” The response datais the plurality of measurements captured by processor 212 from detector222 during the measurement interval. The measurement interval may beanywhere between, for example, about 10 seconds and about 4 minutes. Themeasurement rate may be anywhere between 1 and 100 or more measurementsper second. In one example embodiment, the measurement interval is about2 minutes and the measurement rate is 2 measurements per second. Themeasurements interval and the measurement rate may vary depending upon,among other things, the particular application to which the usecomposition is directed and the corresponding threshold concentrationsof peracid and hydrogen peroxide in the use composition. The measurementrate may also be influenced by the resolution of the electronics.

Once processor 212 collects the response data, processor 212 determinesthe concentrations of peracid and/or hydrogen peroxide in the usecomposition based on the response data (252). This process is describedin more detail herein with respect to FIGS. 3A-3D and FIG. 4. Themeasurement sequence is then complete (254). Processor 212 may then waitfor the next monitoring interval or for a user request and repeat thesequence 240 with a new sample of use composition.

FIG. 10 is a flow chart illustrating an alternative measurement sequence1000 to the above described measurement sequence. Alternativemeasurement sequence 1000 can be carried out by use composition monitor200 or variations on use composition monitor 200 described herein tocollect response data and determine the concentration of peracid and/orhydrogen peroxide in a use composition. In some embodiments, usecomposition monitor may be programmed to determine the concentrations ofperacid and hydrogen peroxide on a periodic basis based on a monitoringfrequency as described above. The monitoring frequency/interval may varydepending on, among other things, the particular application to whichthe use composition is directed and the corresponding thresholdconcentrations of peracid and hydrogen peroxide.

At the start (1002) of each alternative measurement sequence 1000, theprocessor 212 manages preparation of a reagent blank (1004) and collectsthe voltage response of the detector with the reagent blank (1006).These two steps are generally analogous with the above described firsttwo steps (244, 246) of the measurement sequence 240 of FIG. 2. In someembodiments, the measurement of an actual reagent blank need not beperformed during every measurement sequence, but can be performedperiodically, e.g. once per week or month. For such variants, theabsorbance (optical density) of rinsing water during each measurementcycle can be used as a reagent blank (zero absorbance level).

According to the alternative measurement sequence 1000, an expectedconcentration range E for one or more of the analytes is selected(1008). The selection of an expected concentration range E can occurprior to the start of the measurement sequence or at an early stageprior to the use composition sample preparation and analysis steps, e.g.after the preparation of the reagent blank (1004) and collection ofresponse data of the reagent blank (1006). In some embodiments, theselection of the expected concentration range is a static operationwherein a range selected during one measurement sequence or anotheroperation (e.g. the expected range can be pre-programmed) is utilizedfor subsequent measurement sequences.

The expected concentration range selection can be conveyed to thecontroller by user input or memory indicating a specified range, or theselection of a pre-determined range. Pre-determined range selections cancomprise application independent concentration ranges (e.g. selectionbetween “high” and “low” concentration ranges) or concentration rangeskeyed to particular uses, applications, or environments with which themeasurement is associated. For example, application specificconcentrations can comprise: Aseptic bottle rinse comprising 1000-5000ppm peroxyacetic acid and 5000-40,000 ppm hydrogen peroxide, or CentralSanitizer comprising 100-1000 ppm peracid and 100-5000 ppm hydrogenperoxide. Moreover, in some embodiments, the step of selecting theexpected concentration range can comprise an adaptive selection process.In an adaptive selection process, the expected concentration range isselected by measuring the optical response of an initial sample anddetermining whether the response data of the initial sample isappropriate. The controller can then iteratively change the volume ofcomponents of the sample (preferably, the diluent, use composition, orboth diluent and use composition), measuring the optical response of thesample until appropriate response data is collected. In any case, theselected expected concentration range is then used in subsequent stepsto determine the appropriate parameters for calculating accurateconcentration values.

Subsequent to the selection of an expected concentration range (1008),processor 212 manages a sequence of drawing in the constituent parts ofthe sample and dispensing them into the detector line to prepare thesample mixture (1010). According to embodiments of the alternativemeasurement sequence 1000, the expected concentration (E) can determinehow the step of preparing of the sample mixture (1010) is carried out soas to reproducibly generate appropriate response data. Appropriateresponse data, plotted in the form of optical density v. time generallyresembles a data curve such as that shown in FIG. 21. With regard to thepreparation of the sample, the expected concentration range asdetermined above can be utilized to determine the order in which thecomponents of the sample are delivered to the sample/detector line. In apreferred embodiment, the order of sample constituents within the sampleline comprises first carrier, then use composition, then diluent (ifused), then acid (if used), and then reagent, however, generally anyorder can be used.

Moreover, the expected concentration range can be used to determine thevolumes of each of the constituents of the sample. For example, in theoptical analysis of a use composition containing peracid and peroxide inhigh concentrations, the creation of the triiodide complex can exceedthe detection capabilities of the optical sensor. That is, the sensormay not be sensitive enough to detect light passing through the reactedsample, or alternatively the detector can become saturated. In eithercase, appropriate response data cannot be collected and the monitor willnot be capable of producing an accurate concentration reading. Toprevent saturation issues, the sample can be prepared such that thecollected absorbance values are well within the operating range of thedetector. Such preparation can include diluting the use composition byvarying the barrier volume of diluent, e.g. water, between the usecomposition and reagents. For example, FIG. 11 illustrates the effect ofvarying the barrier volume on the response data collected from threesamples 1102, 1104, 1106. Each of the samples 1102, 1104, 1106 compriseda use composition having a peracid concentration of 4000 ppm and aperoxide concentration of 18500 ppm. In the first sample 1102, thebarrier volume comprised 200 microliters of water. In the second sample1104, the barrier volume comprised 250 microliters of water. And in thethird sample 1106, the barrier volume comprised 300 microliters. As canbe seen, the altering of the barrier volume merely vertically shiftedthe response data. If, for example, a monitor includes an opticaldetector that saturates, i.e. is inoperable, at optical densities above1.0, embodiments of the invention would need to take precautions whenpreparing sample so that the response data curve does not exceed anoptical density of 1.0. In such a case, where the expected concentrationrange would result in response data displaying curves such as curve 1104or above, the step of preparing the sample could be modified to increasethe barrier volume, thus lowering the response data curve to the rangeof curve 1106 which provides response data below the saturation value ofthe detector. While this is but one example of how the preparation stepmay depend upon the expected concentration range E, one of ordinaryskill in the art can appreciate many further situations which similarlydepend upon the expected concentration range.

In some embodiments, during the step of preparing the sample (1010) thesample can be mixed. The sample can be mixed prior to delivery or as itis delivered to the detector. Embodiments using a laminar ornon-turbulent flow mixer, such as those described above, provide amixing profile within the mixer/detector line. For example, the mixingprofile of FIG. 12A indicates concentrations of sample components withrespect to time as viewed from a single location along the detectorline, e.g. at a measurement location. Given that the flow rate throughthe detector line is known and generally constant, the graph readilytranslates into a plot of concentrations within the detector as afunction of time. Thus, the mixing profile represents the concentrationsof each sample component at any given time within the detector. In thisexample, a volume of use composition can be seen to bleed back into avolume of acid and reagent as indicated by use composition, acid, andreagent curves 1202, 1204, 1206. That is, for example, the relativeconcentrations of the sample at a detector location on the mixingprofile corresponding to 14 seconds from when the pump was activated areapproximately: 2% use composition, 5% acid, and 18% reagent (KI in thiscase). The remaining 75% of the sample at this location comprisescarrier fluid or a diluent. Percent concentrations as shown in FIG. 12Aare the percentage of nominal concentration delivered to the inputs fromcorresponding lines. FIG. 12B shows data from FIG. 12A in another form,i.e. as a ratios of (1) acid volume relative to volume of usecomposition 1208 and (2) reagent (e.g. KI) volume relative to volume ofuse composition 1210.

According to the present invention, embodiments of methods and devicesfor determining the concentrations of one or more use compositionsundergoing kinetic reactions include obtaining response data from asample over time. Thus, in the alternative measurement sequence 1000 ofFIG. 10, the step of collecting response data (1012) can comprisedelivering the sample mixture to the optical cell such that a desiredmeasurement location along the mixing profile is positioned within theoptical cell. In such embodiments, the measurement location should beselected to provide appropriate response data.

FIGS. 12A-14 can be used to illustrate one way to determine anappropriate lag time, i.e. the determination of when to stop the sampleflow such that the desired measurement location is within the opticalcell. It is generally preferable to have an excess of reagent incomparison with use composition so the reaction of the use compositioncan be fully carried out. With respect to FIGS. 12A and 12B it can beseen that, in the embodiment of the monitor used to generate thatparticular mixing profile, an excess of reagent occurs at approximately9 seconds. Accordingly, this time approximately corresponds with themaximum point 1302 shown in FIG. 13, which represents the opticaldensity v. time plot of a plurality of samples pushed straight throughthe detector line. In addition, FIG. 14 shows the standard deviations ofthe recorded optical densities of the samples of FIG. 13. In somepreferred embodiments, the measurement location is selected atapproximately the local minimum of the standard deviation (FIG. 14) andat a point along the push volume optical density curve (FIG. 13) so asto allow for operation within the dynamic range of the optical sensors.Thus in some embodiments, the measurement location is selected atapproximately 11 seconds from the start of pumping of the sample throughthe detector line. This is the point from which the time derivativeabsorption values start, i.e. corresponding with the start of the linearportions of the response curves of each sample 1102, 1104, 1106 as seenin FIG. 11. For other embodiments and for different concentration levelsof active components within the use composition, different pumping time(lag time) can be selected. In some embodiments, two conditions shouldbe met to select an acceptable lag time: (1) the relative standarddeviation for output signals should be less than a predetermined limit(for example, less than 1%); and (2) the ratios of the acid and thereagent (e.g. KI) concentrations to the use composition concentrationshould not exceed a ratio set for the nominal solutions. For example,from FIG. 12B, it can be seen that at 17 seconds for nominalconcentrations, the acid-to-use composition ratio is approximately 4 andthe reagent-to-use composition ratio is approximately 31. From FIG. 14,it can be seen that the relative standard deviation at this time (17seconds) is less than 1%. Thus, at 17 seconds, in this embodiment, theanalytical device can work with a use composition having componentconcentrations four times greater than those in the use composition thanwas set for the nominal solutions. It will be the nominal ratio for acidand an excess of reagent as required.

The selection of a measurement location along a mixing profile toprovide reproducible appropriate response data can be facilitated byproviding controlled laminar flow mixing of the sample. Controlledlaminar flow mixing is generally accomplished by providing forrepeatable laminar mixing of the components of the sample. To providefor such controlled mixing, it is generally desirable that the laminarflow mixer be maintained at a constant temperature along its entirelength as uneven heating of the sample within the mixer can lead tounpredictable, and undesirable mixing. Thus, embodiments of thetemperature regulated optical sensors described below may be preferablefor carrying out some methods according to embodiments of the invention.

The absorbance of the analyte utilized in this system increases as theanalyte concentration increases. At low and high analyte concentrationthe absorption reaches a minimum or maximum that negatively affects theaccuracy of the measurement. Most analytes have an absorbance curve overa range of wavelengths that allows for light sources with these specificwavelengths to be utilized.

Once detector 222 receives the sample mixture, processor 212 collectsthe response data from detector 222 (1012). In the case of an opticaldetector, the response data is the measured change in the opticalresponse of the detector over time. In some embodiments, detector 222measures response data by measuring the color change (e.g., absorbanceor transmittance) of the sample solution within detector 222 as afunction of time. In other words, the voltage response of detector 222as a function of time corresponds to the amount of light transmittedthrough the sample mixture and hence the color the of the sample mixtureas the chemical reaction progresses. The response data is indicative ofthe concentrations of peracid and hydrogen peroxide in the usecomposition.

Once processor 212 has collected the response data (1012), processor 212determines the concentrations of peracid and/or hydrogen peroxide in theuse composition based on the response data (1014), and according to theexpected concentration E. For relatively low concentrations, thisprocess has described in more detail with respect to FIGS. 3A-3D andFIG. 4. With respect to higher concentrations, the process has beendescribed below. The measurement sequence is then complete (1016).Processor 212 may then wait for the next monitoring interval or for auser request and repeat the sequence 240 with a new sample of usecomposition.

After detector 222 collects the response data, use composition monitor200 may be rinsed and readied for the next monitoring interval (notshown). This may occur either simultaneously with or after theconcentrations of peracid and hydrogen peroxide in the use compositionare determined. Rinsing may also take place prior to preparation of theblank sample to ensure adequate rinsing of the use composition monitor200. The sample line 219A may also be flushed with the use compositionshortly or immediately prior to preparation of the sample mixture toensure that the measurements are taken using the freshest usecomposition and thus help to ensure results that accurately reflect thecurrent concentrations of peracid and/or peroxide in the usecomposition.

Table 1 shows one example implementation of the measurement sequenceshown in FIG. 2. However, it shall be understood that Table 1 shows butone example of many possible measurement sequences, and that theinvention is not limited to this particular implementation.

TABLE 1 Example Measurement Sequence Start Verify water valve is closedVerify sample line valve is closed Select mixer/detector line Dispense2800 microliters Select carrier line Aspirate 2800 microliters carrierSelect mixer/detector line Dispense 2900 microliters Select carrier lineAspirate 1900 microliters Select KI line Aspirate 250 microliters Selectmixer/detector line Dispense 250 microliters Select acid line Aspirate100 microliters Select mixer/detector line Dispense 50 microlitersSelect waste line Dispense 150 microliters Select mixer/detector lineDispense 1500 microliters Collect detector response with reagent blankOpen sample valve Select carrier line Aspirate 2800 microliters Selectmixer/detector line Dispense 2800 microliters Select carrier lineAspirate 1900 microliters Select KI line Aspirate 250 microliters Selectmixer/detector line Dispense 250 microliters Select acid line Aspirate100 microliters Select mixer/detector line Dispense 50 microlitersSelect waste line Dispense 2800 microliters Select carrier line Aspirate1000 microliters Select sample line Aspirate 500 microliters Selectwaste line Dispense 1000 microliters Select sample line Aspirate 500microliters Select waste line Dispense 2800 microliters Select carrierline Aspirate 1800 microliters Select sample line Aspirate 450microliters Select mixer/detector line Close sample valve Dispense 1500microliters Collect response data with sample mixture Select carrierline Aspirate 1000 microliters Select mixer/detector line Dispense 2800microliters Select carrier line Aspirate 2800 microliters Selectmixer/detector line Dispense 2900 microliters Select carrier lineAspirate 2000 microliters Done

Table 2 shows one example implementation of the measurement sequenceshown in FIG. 10. However, it shall be understood that Table 2 shows butone example of many possible measurement sequences, and that theinvention is not limited to this particular implementation.

TABLE 2 Example Alternative Measurement Sequence I. Rinse detector withwater. Rotate stream selector to detector position. Take syringe pumpout of sleep mode. Empty the syringe at a speed of 200 microliters asecond. Take vacuum pump out of sleep mode. Rotate stream selector towater position. Aspirate the syringe full at a speed of 100 microlitersa second. Put vacuum pump in sleep mode. II. Perform zero measurement.Rotate stream selector to detector position. Pump (Push Vol) microlitersout of the syringe at a speed of 100 microliters a second. Zero unitduring (Lag Time) + (Measure Time). III. Flush sample line. Turn on thesample valve. Take vacuum pump out of sleep mode. Rotate stream selectorto water position. Aspirate [(Push Vol) − 600] microliters to thesyringe at a speed of 100 microliters a second. Put vacuum pump in sleepmode. Turn the sample valve off after the sample rinse time expires.Rotate stream selector to sample position. Aspirate 600 microliters tothe syringe at a speed of 50 microliters a second. Rotate streamselector to drain position. Pump 600 microliters out of the syringe at aspeed of 200 microliters a second. Rotate stream selector to sampleposition. Aspirate 600 microliters to the syringe at a speed of 50microliters a second. Rotate stream selector to drain position. Pump 600microliters out of the syringe at a speed of 200 microliters a second.Rotate stream selector to sample position. IV. Dispense sample to thedetector channel. Aspirate 600 microliters to the syringe at a speed of50 microliters a second. Rotate stream selector to drain position. Pump100 microliters out of the syringe at a speed of 100 microliters asecond. Rotate stream selector to detector position. Pump (Sample Vol)microliters out of the syringe at a speed of 100 microliters a second.Rotate stream selector to drain position. Empty the syringe at a speedof 200 microliters a second. V. Partially fill syringe with water. Takevacuum pump out of sleep mode. Rotate stream selector to water position.Aspirate [2400 − (Barrier Vol) − (KI Vol) − (HOAC Vol)] microliters tothe syringe at a speed of 100 microliters a second. Put vacuum pump insleep mode. VI. Aspirate KI Volume Rotate stream selector to KIposition. Aspirate [(KI Vol)] microliters to the syringe at a speed of50 microliters a second. VII. Aspirate HOAC Volume Rotate streamselector to HOAC position. Aspirate [(HOAC Vol)] microliters to thesyringe at a speed of 50 microliters a second. VIII. Aspirate BarrierVolume Take vacuum pump out of sleep mode. Rotate stream selector towater position. Aspirate [(Barrier Vol)] microliters to the syringe at aspeed of 50 microliters a second. Put vacuum pump in sleep mode. IX.Push solution to detector Rotate stream selector to detector position.Pump (Push Vol) microliters out of the syringe at a speed of 100microliters a second. X. Perform measurement Take a reading during (LagTime) + (Measure Time). XI. Rinse detector channel Empty the syringe ata speed of 200 microliters a second. Take vacuum pump out of sleep mode.Rotate stream selector to water position. Aspirate the syringe full at aspeed of 100 microliters a second. Put vacuum pump in sleep mode. Rotatestream selector to detector position. Empty the syringe at a speed of200 microliters a second. XII. Rinse sample line Take vacuum pump out ofsleep mode. Rotate stream selector to water position. Aspirate thesyringe full at a speed of 100 microliters a second. Put vacuum pump insleep mode. Rotate stream selector to sample position. Pump 2000microliters out of the syringe at a speed of 200 microliters a second.Rotate stream selector to drain position. Empty the syringe at a speedof 200 microliters a second. XIII. Prepare unit for next measurementTake vacuum pump out of sleep mode. Rotate stream selector to waterposition. Aspirate the syringe full at a speed of 100 microliters asecond. Put vacuum pump and syringe pump in sleep mode. Turn on the H2Ovalve. Turn the H2O valve off after the water rinse time expires. Returnto step one on reinitiating measurement procedure.

The measurement sequence of Table 2 has been described with reference toa peracid and peroxide use composition monitor having a syringe volumeof 2400 microliters. The variable “Push vol” as used above, canrepresent the volume of liquid pushed through the detector line prior toa measurement or zeroing of the system. This push volume can be selectedto deliver mixed use composition into the optical cell at a measurementlocation along the mixing profile. In some embodiments, this measurementlocation can be a location along the mixing profile where there is amaximum of reagent (e.g. KI) and relative standard deviation of opticalcell readings is at a minimum. The variables “KI Vol,” “HOAC Vol,” and“Sample Vol” represent, respectively, the volumes of reagent (e.g. KI),acid (e.g. acetic acid, if applicable), and use composition deliveredthrough the detector line during a measurement sequence. The variable“Barrier Vol” can represent the volume of barrier liquid (e.g. water)separating the reagent and acid (if applicable) from the use compositionas the measurement sequence starts. Accordingly, in some embodiments,the mixing profile of the measurement sequence can depend upon thevalues selected for these variables. Timing variables used in Table 2include “Lag Time” and “Measurement Time.” The “Lag Time” represents thetime needed to deliver the sample through the detector line such thatthe measurement location along the mixing profile is stopped within theoptical cell. Data collected from the optical cell during the Lag Timeis generally not used in performing a measurement calculation. The“Measurement Time” represents the duration for which the measurementlocation is stopped within the optical cell. Data collected from theoptical cell during the Measurement Time is used to perform themeasurement calculation. Values (volume and/or time) to replace thevariables used above can be selected based upon a variety of factors,including but not limited to, the expected concentration range of theuse composition.

Use composition monitor 200 determines the concentrations of peracidand/or hydrogen peroxide in the use composition using a kinetic assayprocedure. This is accomplished by exploiting the difference in reactionrates between peracid and hydrogen peroxide when using, for example, abuffered iodide reagent to differentiate peracid and hydrogen peroxideconcentrations when both these analyte compounds are present in the usecomposition. Use composition monitor 200 may also determine theconcentrations of peracid and/or hydrogen peroxide in the presence ofother additional ingredients, such as acidulants, one or morestabilizing agents, nonionic surfactants, semi-polar nonionicsurfactants, anionic surfactants, amphoteric or ampholytic surfactants,adjuvants, solvents, additional antimicrobial agents or otheringredients which may be present in the use composition.

In a use composition including hydrogen peroxide and a peracid such asperoxyacetic acid, a buffered iodide changes color as it is oxidized byboth the peroxyacetic acid and the hydrogen peroxide to form triiodideion. However, as the peroxyacetic acid and the hydrogen peroxide in theuse composition compete for the available iodide ions, reaction with theperoxyacetic acid proceeds at a faster rate than the reaction with thehydrogen peroxide, as shown in the following equations:

2CH₃COOOH+(excess) I⁻→I₃ ⁻+2CH₃COOH FASTER

H₂O₂+(excess) I⁻+2H⁺→I₃ ⁻+2H₂O SLOWER

This difference in reaction rates may be exploited to differentiateperacid and hydrogen peroxide concentrations when both these analytecompounds are present in the use composition. An example reaction isdescribed below and the results illustrated in FIGS. 3A-3D. It shall beunderstood, however, that the example below is for illustrative purposesonly and that the invention is not limited to the particular reactionchemistry described in the example below, and that the invention is notlimited in this respect.

EXAMPLE

A buffered potassium iodide reagent was prepared by adding 0.489 g KI to50 ml of 2% KHP (potassium acid phthalate) and diluting to 100 ml withdeionized water. Other suitable buffers would also provide adequatebuffering. For example, phosphate-based buffer prepared from potassiumdihydrogen phosphate and dibasic sodium phosphate could be used tobuffer the reagent to a pH of approximately 5.0 to 6.5. The iodidesolution was tested over the concentration range of 0.025 Molar to 0.075Molar iodide. It shall be understood that other buffer solutions or anunbuffered iodide solution may also be used depending upon theconcentration of acid within the peracid and peroxide in the solution,as will be understood by those of skill in the art.

The samples were tested at room temperature to determine absorbance at365 nm over times ranging from 0 to 114 seconds. In these experiments,absorbance data were acquired using a Cary 100 Bio UV-Visible scanningspectrophotometer (Varian, Inc., Palo Alto, Calif.). The results areshown in Table 3 and plotted in FIGS. 3A-3D.

TABLE 3 ppm POAA in cell Total ppm perox in sample 0.5 0.39 5.39 10.3920.39 35.39 1 0.77 4.77 9.77 9.77 19.77 34.77 2 1.54 5.54 10.54 20.5435.54 4 3.08 7.08 12.08 22.08 37.08

The absorbance vs. time plotted in FIG. 3A shows a substantially linearincrease, which resulted from the reaction of the hydrogen peroxide inthe samples with the iodide ion supplied by the reagent KI solution. Asshown in FIG. 3B, the absorbance at t=0 (A₀) remained constant as theconcentration of peroxide in the sample increased, while the plot of A₀vs. concentration of POAA in FIG. 3C shows a linear relationship, whichsuggested that A₀ is proportional to the concentration of POAA andapparently independent of the concentration of hydrogen peroxide.Referring to FIG. 3D, the slope of the rate of absorbance, A_(t), vs.time curve is proportional to the concentration of peroxide in thesample, and is apparently independent of the concentration of POAA inthe sample.

This Example illustrates that at room temperature, the initialabsorbance at 365 nm of the triiodide complex, measured at time=0seconds, A₀, is independent of the concentration of hydrogen peroxide inthe use composition. The rate of the change in absorbance of thetriiodide complex for time>0 seconds, A_(t), is indicative of theconcentration of hydrogen peroxide. Further, increasing the hydrogenperoxide concentration increases the rate of increase of the absorbanceof the triiodide complex, A_(t). This relationship demonstrates that:(1) the initial absorbance A₀, is dependent on the peroxyacetic acidconcentration and independent of the hydrogen peroxide concentration;and (2) the rate of increase of the absorbance, A_(t), is dependent onthe concentration of hydrogen peroxide and independent of theperoxyacetic acid concentration. The related and competing reactionswith the triiodide complex demonstrate that it is possible tosimultaneously measure the concentration of peroxyacetic acid and theconcentration of hydrogen peroxide in a sample of the use compositionusing a kinetic assay procedure.

FIG. 4 is a flowchart illustrating the procedure by which processor 212determines the concentrations of peracid and hydrogen peroxide fromresponse data obtained by detector 222. As discussed above, the responsedata, when plotted as absorbance versus time, reveals that theabsorbance at t=0 (A₀) is proportional to the concentration of peracidin the use composition. In addition, the rate (slope) of absorbance,A_(t), vs. time is proportional to the concentration of peroxide in thesample.

The absorbance values at each point in time, A_(t), are determined bythe following equations:

A _(t)=−log₁₀ V _(t) /V ₀,

where V_(t) is the voltage response of the detector and V₀ is thevoltage response of the detector measured with the reagent blank.

When the response data has been collected and the absorbance values as afunction of time have been calculated, processor 212 analyzes theresponse data to determine the relationship that best fits the responsedata (302). For example, processor 212 may perform a polynomialregression on the response data to determine the best fit equation. Thepolynomial regression may be a first order equation (linear regression)or may be a higher order equation (generally non-linear but which mayapproximate a linear relationship over certain measurement intervals).

As is known to those of skill in the art, linear regression attempts tomodel the relationship between two variables by fitting a linearequation to observed data. A linear relationship is governed by theequation y=mx+b, where the m is the slope and b is the y-intercept. Itshall be understood, however, that higher order equations may also beused when needed without departing from the scope of the presentinvention. When higher order equations the measurement interval may beadjusted so that the resulting equations approximate a linearrelationship so that a slope may be approximated.

In some embodiments, the regression analysis may be performed in realtime as the response data is collected. In other embodiments, theregression analysis may be performed after all of the response data hasbeen collected.

Once the regression analysis is performed and the best fit line (orhigher order equation) is found (302) the slope and the y-intercept aredetermined (304). In one embodiment, the y-intercept is extrapolatedback (306) to account for a time lag (t_(lag)) which may occur betweenwhen the reagent is mixed with the diluted sample in static mixer 222and when the sample/carrier/reagent mixture actually arrives into thedetector (see 258 in FIG. 2). Because the reaction between the peracidand the reagent(s) occurs quickly (for example, within 1 second), thatreaction may already be complete by the time the sample mixture arrivesin the detector. Thus, there may a delay between the time that thesample mixture arrives in the detector (time t₀) and the time that theperacid reaction takes place (time t₀-t_(lag)). In the embodiment ofFIG. 1, the time t_(lag) is approximately 3 seconds, but may be anywherefrom about 0.5 seconds to about 15 seconds. Since the linearrelationship between absorbance and time is known, the y-intercept maybe extrapolated back in time by an amount equal to t_(lag) to determinethe adjusted y-intercept value (b_(adj)) that is in some embodimentsproportional to the concentration of peracid in the use composition.

Processor 212 then determines the actual concentrations of the peracidand/or the concentration of hydrogen peroxide in the use composition(308). Because the y-intercept and slope are proportional to theconcentration of peracid and hydrogen peroxide, respectively, conversionfactors may be determined which allow calculation of the concentrationsbased on knowledge of the y-intercept and slope of the linearrelationship which best fits the response data. In one embodiment,processor 212 multiplies the y-intercept and slope by predeterminedconversion factors to calculate the actual concentrations of peracid andhydrogen peroxide, respectively, in the use composition. The conversionfactors are determined by calculating the slope and intercepts for knownstandard peracid and hydrogen peroxide samples and using the resultingrelationships to calculate proportionality constants.

In one embodiment, the peracid conversion factor for converting theadjusted y-intercept, b_(adj) into the actual concentration of peracidis 3.39 ppm peracid per absorbance unit when a 1 cm optical cell isused. The peroxide conversion factor for converting the slope, m, intothe actual concentration of hydrogen peroxide is 6692 ppm per absorbanceunit per second when a 1 cm cell is used. The conversion factors may beused to determine the actual concentrations of peracid and/or theconcentration of hydrogen peroxide in the use composition using thefollowing equations:

ppm peracid=A _(t=0)·(peracid conversion factor)=A _(t=0)·3.39,

ppm peroxide=Slope·(peroxide conversion factor)=Slope·6692

where A_(t=0) and the Slope are determined from a polynomial regressionof the absorbance versus time data obtained at 365 nm. The polynomialregression may be, for example, a first order (linear) equation. Thepolynomial regression may also be a higher order (nonlinear) equation.It shall be understood that the above conversion factors are forexemplary purposes only, and that other appropriate conversion factorsmay be used depending upon the volume of sample introduced into thereaction mixture and the extent of dilution of the sample during themixing process within the instrument, and that the invention is notlimited in this respect.

In another embodiment, the actual concentrations of peracid and/orperoxide in the use composition may be determined based upon optimizedhigher order conversion equations. In particular, it has been recognizedthat a linear conversion relationship based upon a single parameter(i.e. peracid concentration=f(A_(t=0)) and peroxideconcentration=f(slope)) does not hold for high concentrations of peracidand/or peroxide. Thus, at higher concentrations, peracid can be said tobe a function of initial absorbance and slope (i.e. peracidconcentration=f(A_(t=0), slope)) and peroxide is a function of slope andinitial absorbance (i.e. peroxide concentration=f(slope, A_(t=0)). Inone example, a higher order conversion equations can take the followingform:

ppm peracid=[K _(1a) +K _(2a) X _(m) +K _(3a) Y _(m) +K _(4a) X _(m)̂(B_(1a))+K _(5a) Y _(m)̂(B _(2a))+K _(6a) X _(m)̂(B _(3a))Y _(m)̂(B_(4a))]̂(B _(5a))

ppm peroxide=[K _(1b) +K _(2b) X _(m) +K _(3b) Y _(m) +K _(4b) X _(m)̂(B_(1b))+K _(5b) Y _(m)̂(B _(2b))+K _(6b) X _(m)̂(B _(3b))Y _(m)̂(B_(4b))]̂(B _(5b))

where X_(m) is the measured initial absorbance A_(t=0) and Y_(m) is themeasured slope. K_(1a)-K_(6a) and B_(1a)-B_(5a) are coefficients withrespect to the peracid concentration. Likewise, K_(1b)-K_(6b) andB_(1b)-B_(5b) are coefficients with respect to the peroxideconcentration. The values of each of the coefficients (K_(1a)-K_(6a),B_(1a)-B_(5a), K_(1b)-K_(6b), and B_(1b)-B_(5b)) can be determinedthrough a calibration process run prior to the operation of the opticalanalysis system or can be otherwise provided.

Some embodiments comprise a method for calibrating an optical analysisinstrument for determination of unknown concentrations of peracid and/orperoxide. For example, some optical analysis instruments include acalibration mode, which determines the values of high order coefficientsnecessary for reconciling measured response data, e.g. absorption data,with actual concentration levels. In such case, a method of calibrationfor an optical analysis instrument can comprise setting the device incalibration mode. The method further comprises preparing a plurality ofcalibration solutions to be analyzed by the instrument. The instrumentobtains response data comprising at least two parameters (e.g. initialabsorbance and time derivative of absorbance) from the calibrationsolutions. An evaluation function can then be constructed with respectto each analyte. The evaluation function can be optimized such thatvalues are determined for coefficients of the evaluation function. Thecoefficient values can then be stored in memory and retained for use ina conversion function such as those described above.

FIG. 15 shows a plot of a set of calibration solutions with respect tosome embodiments of the method of calibration. In this embodiment, a setof nine calibration solutions are indicated. The calibration solutionshave peracid concentrations selected from the set of 1000 ppm, 2500 ppm,and 4000 ppm and peroxide concentrations selected from the set of 5000ppm, 22,500 ppm, and 40,000 ppm. At every peracid concentration adifferent solution has been prepared for each of the peroxideconcentrations resulting in the nine sets indicated in FIG. 15. Ingeneral, the nine solution sets have been selected to be spread outevenly across a peroxide range (5000 ppm to 40,000 ppm) and a peracidrange (1000 ppm to 4000 ppm). Of course, many different combinations orarrangements of calibration solution values can be selected. Forexample, the calibration solutions can be prepared so as not to beevenly distributed across the peracid or peroxide ranges (e.g. in therange above, the peracid data points could be selected from the set of1000 ppm, 1500 ppm and 4000 ppm). Moreover, in some embodiments, thenumber of prepared calibration solutions, and hence data points, can beselected to be more or fewer than the nine shown in this embodiment.Indeed, it is generally true that the more data points selected the moreaccurate the coefficients. In addition, the selected data points for theperacid range need not equal the number of selected data points for theperoxide range (e.g. 20 data points can be selected comprising fourperacid concentrations and five peroxide concentrations). It is not evennecessary that calibration solutions be prepared for every combinationof elements of the sets of peracid and peroxide concentrations.

Once the calibration solutions have been prepared, the optical analysissystem analyzes each solution to generate corresponding response data.FIG. 16 shows exemplary plots of response data corresponding with eachof the data points of FIG. 15. For example, plot 1602 shows the responsedata collected from the analysis of the calibration sample containing4000 ppm peracid and 22,500 ppm peroxide. From this response data,parameter values can be determined. The parameter values selected shouldbe parameters which are known to correspond with the concentrations ofthe analytes. For example, the initial absorbance and the timederivative of absorbance are known to correspond to the concentrationsof peracid and peroxide.

In some embodiments, the values of the parameters of the calibrationsolutions can be used to calculate a high order conversion relationshipbetween the parameters and the analyte concentrations such as thatdescribed above. To calculate the conversion relationships anoptimization process can be used. For example, the optimization processcan comprise constructing evaluation functions for each of the peracidand the peroxide taking the form:

ΔPOA _(i) =POA _(known,i) −[K _(1a) +K _(2a) X _(i) +K _(3a) Y _(i) +K_(4a) X _(i)̂(B _(1a))+K _(5a) Y _(i)̂(B _(2a))+K _(6a) X _(i)̂(B_(3a))Y _(i)̂(B _(4a))]̂(B _(5a)); and

ΔPeroxide_(i)=Peroxide_(known,i) −[K _(1b) +K _(2b) X _(i) +K _(3b) Y_(i) +K _(4b) X _(i)̂(B _(1b))+K _(5b) Y _(i)̂(B _(2b))+K _(6b) X_(i)̂(B _(3b))Y _(i)̂(B _(4b))]̂(B _(5b)),

wherein ΔPOA_(i) is the i^(th) delta value of the peracid, POA_(known,i)is the known concentration of the peracid of the i^(th) calibrationsolution, ΔPeroxide_(i) is the i^(th) delta value of the peroxide,Peroxide_(known,i) is the known concentration of the peroxide of thei^(th) calibration solution, X_(i) is the value of the first parameter(i.e. the initial absorbance, A_(t=0)) for the i^(th) calibrationsolution, and Y_(i) is the value of the second parameter (i.e. theslope) for the i^(th) calibration solution. Then, numerical analysis canbe used to optimize the coefficients K_(1a,b)-K_(6a,b) andB_(1a,b)-B_(5a,b) by minimizing the sums of the squares of thenormalized delta values, e.g. by minimizing the sum of((ΔPOA_(i)/POA_(known,i))̂2) for each i and the sum of((ΔPeroxide_(i)/Peroxide_(known,i))̂2) for each i. Once coefficients havebeen established, they can be stored in memory for use with the above oranother conversion equation.

The above described calculations, according to some embodiments, can becarried out by a processor or other local hardware. Alternatively, thecalculations can be carried out by an external system.

FIGS. 17 and 18 show representative contour plots which illustrate howoptical density (absorbance) and the slope of optical density (timederivative of absorbance) can correlate with peracid and peroxideconcentrations. These contour plots were created from response datagenerated by calibration solutions prepared to correspond with the datapoints of FIG. 15 and shown in FIG. 16. As can be seen in FIG. 17, theperacid concentration (indicated by the contour lines 1702) stillsubstantially varies according to optical density however a deviationcan be seen as the derivative of optical density increases. Likewise,FIG. 18 indicates that, at these higher concentration ranges, peroxideconcentration still heavily correlates with the derivative of opticaldensity, however the slope of the contour lines 1802 indicate that theperoxide concentration varies with optical density as well.

Moreover, it should be noted that in some embodiments, the calibrationsolutions are prepared with reference to the expected concentrationrange E of the use composition. For example, for an expected peracidconcentration range of 1250 ppm to 3750 ppm, and an expected peroxideconcentration range of 5500 ppm to 39,000 ppm, the data points shown inFIG. 15 may be selected. By selecting data points representative ofperacid and peroxide ranges which encompass the expected concentrationrange, the coefficients are likely to strongly represent actualcoefficients at that value. However, a device need not be calibrated toencompass an entire expected range. For example, the expected rangecould be larger than the calibrated range. In such case, the conversionequations may still be used and are likely to provide a concentrationreading that is reasonably accurate. In view of this, some systems mayoperate to store multiple calibrations (i.e. multiple sets of conversioncoefficients or even wholly different conversion equations) such thatdifferent conversion relationships can be selected or triggereddepending upon the expected concentration range or application selected.

In addition, while the above calibration methods have only beendescribed with reference to certain embodiments illustrated herein, oneshould recognize that calibration methods can be used with other opticalanalysis systems. For example, calibration methods such as thosedescribed can be used when the optical characteristic is fluorescence,scattering, or variation of reflective index. In addition, theparameters measured and used to convert response data into analyteconcentrations can include other parameters such as, for example, aderivative with respect to temperature. Moreover, any such derivativesas referenced herein can include first or higher order derivatives.

In another embodiment, the actual concentrations of peracid and/or theconcentration of hydrogen peroxide in the use composition may bedetermined using lookup tables. In that embodiment, table entries for aplurality of possible y-intercepts would correspond to the concentrationof peracid in the use composition and table entries for a plurality ofpossible slopes would correspond to the concentration of hydrogenperoxide in the use composition. In another embodiment, the actualconcentrations of peracid and/or the concentration of hydrogen peroxidein the use composition may be determined using calibration curves orother methods known to those of skill in the art.

The concentrations of peracid and/or the concentration of hydrogenperoxide in the use composition may be used as feedback to control theconcentration of peracid in the use composition. For example, theconcentration of peracid typically must be maintained within a certainrange, or satisfy at least a minimum threshold concentration (theminimum peracid threshold concentration), in order to ensure adequatedisinfecting and/or satisfy governmental regulations. As anotherexample, the concentration of hydrogen peroxide must be kept below amaximum threshold concentration (the maximum peroxide thresholdconcentration). The maximum peroxide concentration in a reuse system isset by the filler manufacturer. This value is based on the maximum levelof peroxide in the solution that can be rinsed from the bottle leavingbehind less than the residual hydrogen peroxide in the bottle, which isan FDA requirement. Once the concentration exceeds the peroxidethreshold concentration, the use composition must be disposed of a newuse composition made.

The peracid and/or peroxide concentrations may be used in any of severalways. The peracid and/or peroxide concentrations may be used as an inputto a network advisory system that provides notifications, reports,alarms and/or advisory information to a field service provider, a localor on-site monitoring site or a centralized local or remote managementsystem. The concentration information may be used to generate reportsconcerning the peracid and/or peroxide concentrations of the usecomposition at or over various points in time. The concentrationinformation may be used to generate notifications, alarms and/or reportsindicative of either a below threshold peracid concentration or an abovethreshold peroxide concentration. Such notifications, alarms and/orreports may include audible alarm(s), visual alarm(s) or electronicallygenerated alarm(s), e-mails, pages, text messages, cell phonecommunications, scripts, etc. The alarms and/or reports may be sent to aremote monitoring site, an on-site monitoring computer, a technicianand/or a field service provider. The notifications, reports and/oralarms may provide information that maintenance, service or repairshould be provided at the monitored facility, and may also provideinformation as to the type of maintenance, service or repair, repairhistory, and/or advisory information designed to aid the technician orfield service provider. As another example, the peracid and/or peroxideconcentrations may be used to control operation (e.g., shutting down) ofa use composition generator or of an end use application. Otherapplications of the peracid and/or peroxide concentrations may also beused.

As shown in FIG. 1, the concentration of peracid and/or theconcentration of hydrogen peroxide in the use composition as determinedby use composition monitor 200 are fed back to controller 100.Controller 100 may then use this concentration information to controlthe concentration of peracid in the use composition, and to monitor theconcentration of hydrogen peroxide in the use composition to ensure itdoes not increase above the maximum peroxide threshold concentration.

FIG. 5 is a flow chart illustrating the process (330) by whichcontroller 100 monitors and/or controls the concentrations of peracidand/or of hydrogen peroxide in the use composition. Controller 100receives the peracid and/or of hydrogen peroxide concentrations (332).Controller 100 compares the received hydrogen peroxide concentrationwith the peroxide threshold concentration (334). If the measuredhydrogen peroxide concentration exceeds the peroxide thresholdconcentration, controller 100 causes the use composition vessel to beemptied of the spent use composition (336). Controller 100 then controlsflow of peracid and diluent into a use composition vessels (not shown)to make a new use composition (338). Controller 100 then waits for thenext monitoring interval, at which point it will receive the mostrecently measured concentrations of peracid and/or hydrogen peroxidefrom use composition monitor 200 (344).

If the hydrogen peroxide concentration does not exceed the peroxidethreshold concentration (334), controller 100 compares the peracidconcentration in the use composition (as determined by use compositionmonitor 200) with the peracid threshold concentration (340). If theperacid concentration in the use composition is below the peracidthreshold concentration, controller 100 may adjust the peracidconcentration in the use composition until it satisfies the peracidthreshold concentration (342). To do this, controller 100 may controlvalves on the peracid concentrate holding tank and/or diluent holdingtank such that a given amount of peracid and/or diluent is added to theuse composition in use composition vessel, causing a resultant increasein the concentration of peracid in the use composition.

FIG. 6 is a schematic diagram illustrating an exploded view of atemperature regulated optical sensor 400. Optical sensor 400 is oneexample of an optical sensor which may be used as the detector 222 ofFIG. 1. As mentioned above, however, it shall be understood that otheroptical sensors/detectors may also be used without departing form thescope of the present invention. Furthermore, other detectors such as pH,ORP, conductivity or other sensors may be used within the scope of theinvention.

At the core of optical sensor 400 is a cell holder 401 which in usecontains an optical cell 402 into which the sample of the usecomposition, the reagent(s) and the carrier are drawn and in which thecalorimetric detection is performed. In this embodiment, optical cell402 is made of glass. However, optical cell 402 may also be made of anyother appropriate material through which optical calorimetric analysismay be performed, such as quartz, sapphire, optical ceramic and otherexamples known to those of skill in the art.

The sample is brought into optical sensor 400 from static mixer 220(FIG. 1) via input tubing 405A and exits optical sensor 400 via outputtubing 405B. Two sets of optical fibers, input fibers 408A and 408B andcorresponding output fibers 408C and 408D, allow optical sensor toperform optical analysis of the sample using multiple wavelengths. Forexample, response data may be obtained using two wavelengths, which mayresult in a more flexible and/or robust system. Wavelength selection isbased on spectral response of the triiodide complex, and may be withinthe range of 350 to 450 nanometers, for example. In one embodiment, atwo wavelength system may utilize the wavelengths 375 nanometers and 405nanometers, for example.

Cell holder 401 has a channel 403 through which optical cell 402 isinserted and resides after assembly of optical sensor 400. Cell holder401 also has first and second optical input ports 404A and 404B forconnection of input optical fibers 408A and 408B. Cell holder alsoincludes first and second optical output ports 404C and 404D (not shownin FIG. 6) for connection of output optical fibers 408C and 408D. Inthis embodiment, cell holder 401 also includes an input cover 409A andan output cover 409B, each having a bore 403B corresponding to centralbore 403A of cell holder 401.

Optical sensor 400 is temperature regulated. Namely, optical sensor 400regulates the temperature within cell holder 401 so as to maintain arelatively cool temperature (compared to room temperature) at whichoptical analysis of the use composition sample takes place. Analysis ofthe use composition sample at low temperature is done for severalreasons. Rates of chemical reactions are temperature dependent. Controlof the temperature at which the kinetic measurements are made precludesthe need for temperature lookup tables. In addition, the rates ofchemical reactions increase with increasing temperature. As the reactionbetween iodide and hydrogen peroxide is slower than the reaction betweenperacid and iodide this effect may be enhanced at lower temperatures.Although lower temperatures are by no means required for the presentinvention, subambient temperatures may enhance the difference inreaction rates. Thus, in some embodiments, the measurements may be takenwith the sample mixture at ambient temperatures (generally between about20° C. and 25° C.). In other embodiments, subambient temperatures (e.g.,less than 25° C.) may be used. Depending upon the temperature of thelocation where the measurements are to take place, the sample mixturemay be cooled to temperatures approaching the freezing temperature ofwater (for example, as low as about 5° C.). In general, the temperatureat which measurements are taken may be in the range of 5 to 25° C., ormore narrowly between 10 and 18° C.

To measure the temperature of the sample mixture, optical sensor 400includes a temperature sensor 406 placed within a slot 407 of cellholder 401. Temperature sensor 406 is positioned within slot 407 so asto sense the temperature at or very near the surface of optical cell402, resulting in a relatively accurate reading of the temperature ofthe use composition sample contained within optical cell 402. A firstinsulation plate 411 includes a cut out 410 substantially sized toreceive cell holder 401, first and second input ports 404C and 404Dcorresponding to first and second input ports 404A and 404B of cellholder 401, and a channel 403C corresponding to channel 403A of cellholder 401.

At least one thermoelectric module 412 (two in this example,thermoelectric modules 412A and 412B) control the internal temperatureof optical sensor 400 so as to maintain the cooled temperature of thesample mixture. In this embodiment, thermoelectric modules 412A and 412Bare fitted within corresponding cutouts 416A and 416B of a secondinsulation plate 413. A third insulation plate 414 provides for furtherinsulation of the optical cell 402. A support plate 415 provides anouter wall for optical sensor 400.

Heat sink 417 and fan 418 draw heat away from cell holder 401 to so asto maintain a relatively constant internal temperature at or nearoptical cell 402 where optical analysis of the sample of the usecomposition takes place. A third insulation plate 414 provides forfurther insulation of the optical cell 402. A support plate 415 providesan outer wall for optical sensor 400.

In the embodiment of FIGS. 6A-6D, the sample of the use composition, thereagent and the carrier are mixed in static mixer 222 as shown inFIG. 1. As discussed above the peracid concentration is proportional tothe adjusted y-intercept, b_(adj), where b_(adj) is extrapolated backfrom the time that the sample mixture arrives in the detector (time t₀)to the time that the reaction takes place (time t₀-t_(lag)) using theknown linear relationship between absorbance and time for the samplemixture.

In another embodiment, optical sensor 400 includes an internal mixerlocated within optical cell 402 to reduce the time t_(lag) between whenthe sample mixture arrives in the detector (time t₀) to the time thatthe reaction takes place (time t₀-t_(lag)). One example of such anembodiment is shown in FIGS. 7A and 7B.

FIG. 7A illustrates an optical cell 420 with an internal mixer 421, andFIG. 7B is a schematic diagram illustrating an exploded view of anoptical sensor 430 having two input ports incorporating the optical cell420 with internal mixer 421 of FIG. 7A. In order to decrease the timebetween which the diluted use solution and the reagent(s) are mixed andthe resulting sample mixture is introduced into the optical cell foranalysis, optical cell 420 is fabricated to include a mixer cavity 422sized to receive a static mixer 421. Static mixer is inserted into mixercavity 422 in the direction indicated by arrow 424. Optical cell 420also includes an analysis channel 423 in which the sample mixture isanalyzed. In this embodiment optical cell 420 is made of glass but mayalso be made of any other material appropriate for conducting opticalanalysis, such as quartz, sapphire or optical ceramic.

To accommodate optical cell 420 with internal mixer 421, the embodimentshown in FIG. 1 is modified so as not to include static mixer 220.Instead, the diluted use solution and the reagent(s) are simultaneouslydispensed directly into detector 222, which in this case would beimplemented using an embodiment of an optical sensor 430 such as thatshown in FIG. 7B.

The diluted use solution and the reagent(s) are simultaneously dispenseddirectly into optical sensor 430 via use solution input tubing 405C andreagent solution input tubing 405D. Cover 422 is modified from cover309A in FIG. 6 to include two input ports 425A and 425B (425B notvisible in FIG. 7B). The diluted use solution and the reagent(s) arethus simultaneously dispensed directly into static mixer 421. As thediluted use solution and the reagent(s) are dispensed through staticmixer 421 and into analysis channel 423, they are mixed and begin toreact. By incorporating the mixer to be immediately adjacent analysischannel 423 of the optical cell, the time lag t_(lag) may be reduced,resulting in a more accurate determination of the peracid concentrationin the use solution.

FIG. 8 illustrates a front cross sectional view of the example cellholder 401 shown in FIGS. 6 and 7B. As discussed above, cell holder 401includes a channel 406 into which the optical cell is received, slot 407into which temperature sensor 406 is received, first and second opticalinput ports 404A and 404B and first and second optical output ports 404Cand 404D. The diameter of channel 406 is determined based at least inpart on the desired sensitivity of the measurements to be taken. Forexample, channel 406 may have a diameter of approximately 6 mm and theinternal channel of optical cell may have a diameter from approximately1 mm to approximately 3 mm.

FIG. 9 illustrates a front cross sectional view of another embodiment ofa cell holder 430. In this embodiment, cell holder 430 is designed toreceive the sample mixture directly without requiring insertion of aseparate optical cell. In this embodiment, cell holder 430 may befabricated from any suitable material, such as stainless steel, forexample, passivated stainless steel 316, or optical ceramic. Cell holder430 includes a channel 432, slot 407 into which temperature sensor 406is received, first and second optical input ports 404A and 404B andfirst and second optical output ports 404C and 404D. The inner part ofchannel 432 of cell holder 430 further includes multiple subchannelseach having a different diameter. The mixer subchannel 433 is sized toreceive a static mixer in a manner similar to that described above withrespect to FIGS. 6, 7A and 7B. First analysis subchannel 434 ispositioned in the optical path created by first optical input port 404Band first optical output port 404D. Second analysis subchannel 435 ispositioned in the optical path created by second optical input port 404Band second optical output port 404D. The differing diameters of firstand second analysis subchannels 434 and 435 provide for differingsensitivity in absorbance measurement. For example, in one embodiment,subchannel 434 may have a diameter of 3 mm and subchannel 435 may have adiameter of 1 mm, for example.

FIG. 19 shows a modified cell design for obtaining appropriate responsedata according to some embodiments of the invention. One problem withmany detector line arrangements is turbulence. Turbulence can be causedby numerous conditions within the analysis system. Disturbances insample flow can occur at tubing-device interfaces due to variations inthe tolerance of the coupling. In addition, variations of the innerdiameter of the tubing can produce vortexes which change the mixingefficiency and uniformity of the reaction mixture inside of the detectorline. A further source of sample turbulence is the mechanism of samplemixing. Some mixers operate by subjecting the reactants to turbulence,for example, static mixers or a T-junction mixers. If the turbulenceinduced to mix the sample by such mixers is present when the samplereaches the optical cell, measurement repeatability can be negativelyimpacted. Finally, reactions involving reagents, carriers, and usecompositions having different specific gravities can exhibit regions ofvariable mixing, enhancing the effect of turbulence within an opticaldetection system.

FIGS. 20 and 21 illustrate examples of the effect of turbulence onresponse data collected from systems according to embodiments of theinvention. FIG. 20 shows response data from a system such as thosedescribed above. FIG. 21 shows response data from an analysis systemthat is substantially turbulence free according to some embodiments. Theresponse data 2002 of FIG. 20 shows significant oscillations anddisturbances during the measurement period 2004 (i.e. the period wherethe measurement locations along the measurement profile is stoppedwithin the cell). These oscillations can introduce error into theregression analysis leading to less accurate results. Further,oscillations can introduce random error into measurement proceduressignificantly reducing repeatability. In contrast, the response data2102 of FIG. 21 is generally oscillation free during the measurementperiod 2104. According to some preferred embodiments of the invention,FIG. 21 is representative of “appropriate response data.” Moregenerally, the methods and devices for turbulence reduction describedherein can be particularly beneficial for optical analysis of kineticchemistries. This is especially true of kinetic assay procedures usingstopped flow analysis.

In some embodiments, improvements in accuracy and repeatability ofmeasurement data can be achieved by the use of laminar flow mixing incombination with a detector line and an optical cell designed forreduced-turbulence. In one such system, the turbulence reduction systemcomprises a single length of tubing from the multiport valve to thedrain. The tubing is fluidly connected to the multiport valve, passesthrough the optical cell, and connects to or empties into the drain. Insome embodiments, laminar flow mixing is introduced along the tubingbetween the multi-port valve and the optical cell. Laminar flow mixingcan be accomplished by, for example, coiling a length of the tubing. Insome embodiments, the laminar flow mixing coil can comprise a coilhaving a diameter of approximately 3 inches. No intermediate connectionpoints or junctions are positioned along the tubing, thus avoidingsample disturbance caused by variations in the tolerance of thecoupling. Moreover, the tubing should be free of sharp turns or kinks assuch features can introduce turbulence to the sample.

Referring back to FIG. 19, the optical cell 1900 shown can reduce sampleturbulence by allowing for the use of a single tubing 1902 having asubstantially constant diameter along the entire length of the detectorline (i.e. from multiport valve 218 to waste line 224 of FIG. 1). Inthis embodiment, the optical cell 1900 comprises a cell body 1904positioned about the detector line tubing 1902. In some embodiments, theoptical cell is designed to allow the tubing 1902 to pass through thecell body 1904 in a substantially straight path. Cell designs seeking toincrease the optical path length by providing sharp turns or bendswithin the detector line (e.g. a Z-cell) should generally not be used.Such sharp turns or bends within the detector line can cause turbulenceof the sample as described above.

The optical cell 1900 of FIG. 19 further includes two emitters 1906 andtwo detectors 1908 positioned within the cell body 1904 about atransparent portion of the tubing 1902. Each detector 1908 is positionedopposite an emitter 1906 such that the detector can receive lightdirected along an optical path 1910 by the emitter. The optical paths1910 traverse the transparent portion of the detector line tubing 1902and therefore pass through sample contained therein. In someembodiments, the emitter comprises a wave guide (e.g. a fiber opticelement) connected to a light source (e.g. a laser or light emittingdiode) which is isolated from the optical cell body. By contrast, insome embodiments, the emitter comprises a light source directlyinstalled within the cell body. Likewise, the detector can comprise awave guide connected to an optical detector isolated from the opticalcell body or can be directly installed within the cell body. In someembodiments, the transparent portion of the tubing 1902 comprises but aportion of an otherwise opaque tube. Alternatively, in some embodiments,the entire length of the tubing 1902 is transparent, the tube comprisinga polymer, e.g. a fluoropolymer such as, for example,polytetrafluoroethylene, i.e. Teflon.

FIGS. 22A and 22B show additional views of a cell body 1904, such asthat of FIG. 19. The cell body 1904 includes a first pathway 2202 toreceive the detector line tubing. A second pathway 2204 passes the cellbody 1904 and intersects the first pathway 2202 therewithin. The secondpathway 2204 is adapted to receive an emitter/detector pair such asthose shown in FIG. 19. The shown embodiment further includes anadditional pathway 2204′ intersecting the first pathway 2202 forreceiving an additional emitter/detector pair. The second and additionalpathways 2204, 2204′ are oriented generally perpendicular to the firstpathway 2202. While embodiments of the cell body have been shown toinclude two detector/emitter pairs, one should recognize that cellbodies according to embodiments of the invention can include one or morethan two detector/emitter pairs. Moreover, it should be recognized thatthe turbulence reduction systems and optical cell designs describedabove can be used with other sample preparation systems.

Some embodiments of peracid/peroxide monitors can further be optimizedfor use as an on site monitor. That is, there is a need for accurate andreliable sensors to measure peracid and peroxide concentrations whenambient temperature can vary in wide range. Unstable temperature insideof a system have been found to contribute to random variations inconcentration readings. More particularly, the absorbance of theabove-described analytical solutions used in flow injection canexperience changes in absorbance if temperatures of sample and reagentare not repeatable and not stable. Potential causes of such temperatureinstability include environmental temperature variances and locallygenerated heat and air flow from components of the measurement systemsuch as pumps, step motors, and controllers within the monitor. Thus,some embodiments include additional features to isolate the sample frompotential heat sources at all stages of operation and to facilitate useof monitors and methods according in various operating environments. Inaddition, systems according to some embodiments provide means foradjusting or stabilizing the temperature of sample prior to delivery tothe detector to avoid the inconsistencies associated with in fieldoperation.

An embodiment of an optical sensor and sample preparation area (mixingcoil) optimized for use as an on site monitor is shown in FIGS. 23-25.The temperature-regulated optical sensor 2300 generally comprises a cellhousing 2302 installed within an insulated cavity 2304 of an insulatingenclosure 2306. The cell housing 2302 comprises a thermally conductivematerial and can be generally of the form of the above described cellhousings. A sample line can enter the insulated cavity through an entryport in a mounting plate 2308 or wall of the enclosure. Once within theinsulated cavity 2304, the sample line can be coiled about a spool 2310contained therein to provide a non turbulent mixing coil. The spool 2310can be mounted to the cell housing 2302 and likewise comprise athermally conductive material. In this manner, the spool 2310 can drawheat from or deliver heat to sample within the sample line as it passesthrough the mixing coil. Heat can then pass through the thermallyconductive cell housing 2302 and out of the system 2300 via a connectedheat sink 2312. The sample line then passes through bore 2314 within thecell housing 2302 where emitter/detectors installed in emitter detectorpathways 2316 can be used to analyze the sample. The sample line canthen deliver the sample out of the optical cell 2302 via an exit portwithin the mounting plate 2308 or enclosure wall.

Further, embodiments of the improved optical sensor can include athermoelectric heat transfer element (not shown) installed within anopening in the mounting plate 2308 and between the cell housing 2302 andan exterior surface 2320 of the enclosure 2306. Heat sink 2312 can becoupled with the thermoelectric heat transfer element. Thethermoelectric heat transfer element can comprise any such devicecapable of effectuating heat transfer (uni- or bi-directional) under theapplication of an electrical current or voltage. In a preferredembodiment, the thermoelectric heat transfer element comprises a Peltierdevice, however, other devices are envisaged. Still further, someembodiments can include a fan (not shown) coupled to the device so as todirect air about the heat sink 2312 to further facilitate heat transferfrom the device.

Embodiments of the optical cell can be controlled by a controller. Insome embodiments, the controller is processor 212 of FIG. 1. Thecontroller can regulate the thermoelectric heat transfer element and fanto control the temperature of the cell. A temperature sensor 2318 can becoupled with the cell housing or elsewhere within the cell to providefeedback to the controller for temperature regulation purposes. In somepreferred embodiments, the temperature of the cell and samplepreparation area (coil) is controlled to be approximately 24 degreesCelsius. In such case, embodiments can provide for stable operationwithin environmental temperatures ranging from approximately 10 degreesCelsius to approximately 30 degrees Celsius (e.g. 15 degrees C. to 28degrees C.). In some cases, system stability can be improved by a factorof two to three. For example, deviations were not more than 7% for POAfrom concentrations of 1750 ppm to 2500 ppm and hydrogen peroxide from5000 ppm to 40,000 ppm.

The compositions described herein may be used for a variety of domesticor industrial applications, e.g., to reduce microbial or viralpopulations on a surface or object or in a body or stream of water. Thecompositions may be applied in a variety of areas including kitchens,bathrooms, factories, hospitals, dental offices and food plants, and maybe applied to a variety of hard or soft surfaces having smooth,irregular or porous topography. Suitable hard surfaces include, forexample, architectural surfaces (e.g., floors, walls, windows, sinks,tables, counters and signs); eating utensils; hard-surface medical orsurgical instruments and devices; and hard-surface packaging. Such hardsurfaces may be made from a variety of materials including, for example,ceramic, metal, glass, wood or hard plastic. Suitable soft surfacesinclude, for example paper; filter media, hospital and surgical linensand garments; soft-surface medical or surgical instruments and devices;and soft-surface packaging. Such soft surfaces may be made from avariety of materials including, for example, paper, fiber, woven ornonwoven fabric, soft plastics and elastomers. The compositions may alsobe applied to soft surfaces such as food and skin (e.g., a hand). Theuse compositions may be employed as a foaming or nonfoamingenvironmental sanitizer or disinfectant.

The compositions may be included in products such as sterilants,sanitizers, disinfectants, preservatives, deodorizers, antiseptics,fungicides, germicides, sporicides, virucides, detergents, bleaches,hard surface cleaners, hand soaps, waterless hand sanitizers, and pre-or post-surgical scrubs.

The compositions may also be used in veterinary products such asmammalian skin treatments or in products for sanitizing or disinfectinganimal enclosures, pens, watering stations, and veterinary treatmentareas such as inspection tables and operation rooms. The compositionsmay be employed in an antimicrobial foot bath for livestock or people.

The compositions may be employed for reducing the population ofpathogenic microorganisms, such as pathogens of humans, animals, and thelike. The compositions may exhibit activity against pathogens includingfungi, molds, bacteria, spores, and viruses, for example, S. aureus, E.coli, Streptococci, Legionella, Pseudomonas aeruginosa, mycobacteria,tuberculosis, phages, or the like. Such pathogens may cause a varietiesof diseases and disorders, including Mastitis or other mammalian milkingdiseases, tuberculosis, and the like. The compositions may reduce thepopulation of microorganisms on skin or other external or mucosalsurfaces of an animal. In addition, the compositions may kill pathogenicmicroorganisms that spread through transfer by water, air, or a surfacesubstrate. The composition need only be applied to the skin, otherexternal or mucosal surfaces of an animal water, air, or surface.

The compositions may also be used on foods and plant species to reducesurface microbial populations; used at manufacturing or processing siteshandling such foods and plant species; or used to treat process watersaround such sites. For example, the compositions may be used on foodtransport lines (e.g., as belt sprays); boot and hand-wash dip-pans;food storage facilities; anti-spoilage air circulation systems;refrigeration and cooler equipment; beverage chillers and warmers,blanchers, cutting boards, third sink areas, and meat chillers orscalding devices. The compositions may be used to treat producetransport waters such as those found in flumes, pipe transports,cutters, slicers, blanchers, retort systems, washers, and the like.Particular foodstuffs that may be treated with compositions includeeggs, meats, seeds, leaves, fruits and vegetables. Particular plantsurfaces include both harvested and growing leaves, roots, seeds, skinsor shells, stems, stalks, tubers, corms, fruit, and the like. Thecompositions may also be used to treat animal carcasses to reduce bothpathogenic and non-pathogenic microbial levels.

The composition may be useful in the cleaning or sanitizing ofcontainers, processing facilities, or equipment in the food service orfood processing industries. The compositions may be used on foodpackaging materials and equipment, including for cold or hot asepticpackaging. Examples of process facilities in which the compositions maybe employed include a milk line dairy, a continuous brewing system, foodprocessing lines such as pumpable food systems and beverage lines, etc.Food service wares may be disinfected with the compositions. Forexample, the compositions may also be used on or in ware wash machines,dishware, bottle washers, bottle chillers, warmers, third sink washers,cutting areas (e.g., water knives, slicers, cutters and saws) and eggwashers. Particular treatable surfaces include packaging such ascartons, bottles, films and resins; dish ware such as glasses, plates,utensils, pots and pans; ware wash machines; exposed food preparationarea surfaces such as sinks, counters, tables, floors and walls;processing equipment such as tanks, vats, lines, pumps and hoses (e.g.,dairy processing equipment for processing milk, cheese, ice cream andother dairy products); and transportation vehicles. Containers includeglass bottles, PVC or polyolefin film sacks, cans, polyester, PEN or PETbottles of various volumes (100 ml to 2 liter, etc.), one gallon milkcontainers, paper board juice or milk containers, etc.

The compositions may also be used on or in other industrial equipmentand in other industrial process streams such as heaters, cooling towers,boilers, retort waters, rinse waters, aseptic packaging wash waters, andthe like. The compositions may be used to treat microbes and odors inrecreational waters such as in pools, spas, recreational flumes andwater slides, fountains, and the like.

A filter containing a composition may reduce the population ofmicroorganisms in air and liquids. Such a filter may remove water andair-born pathogens such as Legionella.

The compositions may be employed for reducing the population ofmicrobes, fruit flies, or other insect larva on a drain or othersurface.

The compositions may also be employed by dipping food processingequipment into the use solution, soaking the equipment for a timesufficient to sanitize the equipment, and wiping or draining excesssolution off the equipment. The compositions may be further employed byspraying or wiping food processing surfaces with the use solution,keeping the surfaces wet for a time sufficient to sanitize the surfaces,and removing excess solution by wiping, draining vertically, vacuuming,etc.

The compositions may also be used in a method of sanitizing hardsurfaces such as institutional type equipment, utensils, dishes, healthcare equipment or tools, and other hard surfaces. The composition mayalso be employed in sanitizing clothing items or fabrics which havebecome contaminated. The composition is contacted with any contaminatedsurfaces or items at use temperatures in the range of about 4° C. to 60°C., for a period of time effective to sanitize, disinfect, or sterilizethe surface or item. For example, the composition may be injected intothe wash or rinse water of a laundry machine and contacted withcontaminated fabric for a time sufficient to sanitize the fabric. Excesscomposition may be removed by rinsing or centrifuging the fabric.

The compositions may be applied to microbes or to soiled or cleanedsurfaces using a variety of methods. These methods may operate on anobject, surface, in a body or stream of water or a gas, or the like, bycontacting the object, surface, body, or stream with a composition.Contacting may include any of numerous methods for applying acomposition, such as spraying the composition, immersing the object inthe composition, foam or gel treating the object with the composition,or a combination thereof.

The composition may be employed for bleaching pulp. The compositions maybe employed for waste treatment. Such a composition may include addedbleaching agent.

Other hard surface cleaning applications for the compositions includeclean-in-place systems (CIP), clean-out-of-place systems (COP),washer-decontaminators, sterilizers, textile laundry machines, ultra andnano-filtration systems and indoor air filters. COP systems may includereadily accessible systems including wash tanks, soaking vessels, mopbuckets, holding tanks, scrub sinks, vehicle parts washers,non-continuous batch washers and systems, and the like.

Although specific embodiments of a dispenser system have been shown anddescribed, it shall be understood that other embodiments could besubstituted therefore without departing from the scope of the presentinvention. Various embodiments of the invention have been described.These and other embodiments are within the scope of the followingclaims.

1. A method for determining a concentration of a peracid and aconcentration of a peroxide within a use composition, comprising:selecting an expected concentration range within which one or both ofthe concentrations of the peracid and the peroxide are expected to fall,the expected range depending upon an application employing the usecomposition; preparing a sample within a sample line, the samplecomprising the use composition, a diluent, and one or more reagents;mixing the sample within the sample line to provide a sample mixturehaving a mixing profile representative of the amount of the usecomposition, the diluent, and the reagents within the sample; deliveringthe sample mixture to an optical cell, such that a measurement locationalong the mixing profile is positioned within the optical cell, themeasurement location having been selected to provide appropriateresponse data; measuring an optical response of the sample mixture atthe measurement location for a period of time, thereby obtainingresponse data indicative of absorbance of the sample at the measurementlocation as a function of time; and determining the concentration of theperacid and the concentration of the peroxide in the use compositionbased on the response data, wherein, one or more of the steps ofpreparing, mixing, delivering, measuring, and determining depend uponthe expected concentration range.
 2. The method of claim 1, wherein theapplication comprises aseptic cleansing for bottling lines havingperacid concentration from 1000 parts per million (ppm) to 5000 ppm andperoxide concentration from 5000 ppm to 40,000 ppm.
 3. The method ofclaim 1, wherein the application comprises cleansing of dairy equipmenthaving peracid concentration from 100 ppm to 1000 ppm and peroxideconcentration from 100 ppm to 5000 ppm.
 4. The method of claim 1,wherein the expected concentration range is from 5 ppm peracid to 500ppm peracid.
 5. The method of claim 1, wherein the expectedconcentration range is from 500 ppm peracid to 10,000 ppm peracid. 6.The method of claim 6, wherein the expected concentration range is from1000 ppm peracid to 5000 ppm peracid.
 7. The method of claim 1, whereinthe diluent comprises water.
 8. The method of claim 1, wherein the oneor more reagents includes an iodide solution with the pH adjusted to analkaline range.
 9. The method of claim 1, wherein the one or morereagents includes potassium iodide.
 10. The method of claim 1, whereinthe sample further comprises a dilute acid.
 11. The method of claim 10,wherein the dilute acid includes acetic acid.
 12. The method of claim 1,wherein the step of selecting the expected concentration range comprisesan adaptive selection process.
 13. The method of claim 12, wherein theadaptive selection process comprises: measuring the optical response ofan initial sample comprising a volume of the use composition, a volumeof the diluent, and a volume of the one or more reagents; determiningwhether the response data of the initial sample is appropriate; anditeratively changing the volume of use composition, the volume ofdiluent, or the volumes of use composition and diluent used in thepreparation of the sample and measuring the optical response of thesample until appropriate response data is collected.
 14. The method ofclaim 1, wherein the step of preparing the sample comprises: loading avolume of the use composition within the sample line; then loading avolume of diluent within the sample line; then loading a volume of anacid within the sample line; and then loading a volume of reagent withinthe sample line.
 15. The method of claim 1, wherein the step ofpreparing the sample depends upon the expected concentration range. 16.The method of claim 15, wherein when the expected peracid concentrationrange is from 1000 ppm peracid to 5000 ppm peracid, the step ofpreparing the sample comprises: loading from 50 microliters to 200microliters of the use composition within the sample line; then loading50 microliters to 500 microliters of the diluent within the sample line;then loading 50 microliters to 200 microliters of acetic acid within thesample line; and then loading 50 microliters to 200 microliters ofpotassium iodide within the sample line.
 17. The method of claim 1,wherein the step of preparing the sample comprises: loading the usecomposition into the sample line; loading the reagents and the barrierwithin a separate holding line; and coupling the separate holding linewith the sample line to load the barrier and the reagents into thesample line.
 18. The method of claim 1, wherein the step of mixing thesample comprises providing for laminar mixing of the sample.
 19. Themethod of claim 18, wherein the laminar mixing is provided by deliveringthe sample through a mixing coil.
 20. The method of claim 1, the step ofdelivering the sample to the optical cell comprising stopping the samplewithin the cell.
 21. The method of claim 1, wherein the measuringlocation is selected based upon the expected concentration range. 22.The method of claim 1, wherein the measuring location is selected alongthe mixing profile where there is an excess of one or more of thereagents.
 23. The method of claim 1, wherein the measuring location isselected along the mixing profile where a standard deviation of theresponse data is at a minimum.
 24. The method of claim 1, wherein theoptical cell comprises a reduced-turbulence optical cell.
 25. The methodof claim 1, wherein the step of measuring the optical response comprisesselecting a measurement wavelength that corresponds to the expectedconcentration range.
 26. The method of claim 1, wherein the step ofdetermining the concentration of the peracid and the concentration ofthe peroxide in the use composition includes: determining a best fitlinear relationship corresponding to the response data wherein the bestfit linear relationship includes a slope and a y-intercept; andselecting conversion relationships for converting the slope and they-intercept to the peracid concentration and the peroxide concentration,wherein the selection of the conversion relationships depends upon theexpected concentration range.
 27. The method of claim 26, wherein whenthe expected peracid concentration range is less than 500 ppm peracid,the conversion relationship for the peracid concentration is a linearrelationship relative to the y-intercept and the concentrationrelationship for the peroxide concentration is a linear relationshiprelative to the slope.
 28. The method of claim 26, wherein when theexpected peracid concentration range is greater than or equal to 500 ppmperacid, the conversion relationship for the peracid concentrationdepends upon both the slope and the y-intercept and the concentrationrelationship for the peroxide concentration depends upon both the slopeand the y-intercept.
 29. The method of claim 1, further comprising thestep of calculating a plurality of calibration coefficients by (1)measuring an optical response of a plurality of calibration samples,each calibration sample having a known concentration of peracid and aknown concentration of peroxide, and (2) optimizing a system ofequations including the calibration coefficients based upon the measuredoptical responses of the calibration samples, wherein the calibrationcoefficients can then be used in the step of determining theconcentrations of the peracid and the peroxide based upon the responsedata.
 30. The method of claim 29, wherein the known concentrations ofthe peracid and the peroxide are within the expected concentrationrange.
 31. The method of claim 1, wherein the steps of mixing thesample, delivering the sample, and measuring the optical response areperformed within a temperature-regulated local environment.
 32. A systemfor determining a concentration of a peracid and a concentration of aperoxide within a use composition over a wide concentration range, thesystem comprising: an optical detector that obtains response data from asample including a volume of the use composition, a volume of a diluent,and a volume of at least one reagent, wherein the response data isindicative of the concentration of the peracid and the concentration ofthe peroxide; and a processor connected to the optical sensor, andconfigured to determine the concentration of the peracid and theconcentration of the peroxide based on the response data, wherein thedetermination of the concentrations of the peracid and the peroxidedepend upon an expected peracid concentration range within the wideconcentration range.
 33. The system of claim 32, wherein the opticaldetector is a reduced-turbulence optical detector.
 34. The system ofclaim 32, further comprising a laminar flow mixer for mixing the sample.35. The system of claim 34, wherein the mixer and the optical detectorare temperature regulated.
 36. The system of claim 32, wherein the wideconcentration range is from 0 ppm peracid to 10,000 ppm peracid.
 37. Thesystem of claim 32, wherein when the expected peracid concentrationrange is from 500 ppm to 5000 ppm, the processor determines theconcentration of the peracid as a function of a y-intercept and a slopeof the response data and the processor determines the concentration ofthe peroxide as a function of the slope and the y-intercept of theresponse data.
 38. The system of claim 32, wherein when the expectedperacid concentration range is from 0 ppm to 500 ppm, the processordetermines the concentration of the peracid as a function of ay-intercept of the response data and the processor determines theconcentration of the peroxide as a function of a slope of the responsedata.